Disperse dyes of the azobenzene series



United States Patent US. Cl. 260-207 10 Claims ABSTRACT OF THE DISCLOSURE This invention relates to dyes of the 4-nitro-2'-acylamino-4'-dialkylamino-5'-alkoxy-1,1' azobenzene series which are substituted by at least one formyloxy group and have high afiinity from aqueous dispersion for textiles made of synthetic or semi-synthetic materials of hydrophobic character and high molecular Weight. On these substrates the dyes give blue dyeings having excellent allround fastness properties.

The new dyes are of the formula where X stands for a nitro or cyano group, Y for a chlorine or bromine atom or the nitro group, R for a methyl or ethyl radical, R for a fi-formyloxyethyl, B- or 'y-formyloxypropyl, B,'y-diformyloxypropyl, B-formyloxy-y-chloropropyl, p-formyloxy-y-bromopropyl or fi-formyloxy-ycyanopropyl radical, R for a methyl, ethyl, propyl, butyl, cyanalkyl or alkoxycarbonylalkyl group or for one of the significances of R and R for a hydrogen atom or an alkyl or alkoxy radical, and where the alkyl and alkoxy radicals contain 1, 2, 3 or 4 carbon atoms and may be substituted by non-water-solubilizing substituents.

The preferred substituents on the alkyl and alkoxy radicals are chlorine or bromine atoms, cyano, phenyl, phenyloxy, acetyl or benzoyl radicals.

The preferred dyes conform to the formula where R R X and Y have the meanings assigned to them in the foregoing, R stands for an unsubstituted alkyl group having 1, 2, 3 or 4 carbon atoms, or a ,9- cyanethyl, ,B-cyanopropyl, fi-methoxycarbonyl or 54,8- methoxyethoxycarbonyl)-ethyl radical or for one of the meanings of R and R for a hydrogen atom, or a methyl, ethyl, propyl, methoxy, ethoxy, chloromethyl, chloroethyl, bromomethyl, bromoethyl, dichloroethyl, dibromo ethyl, cyanomethyl, phenoxymethyl, fl-chloroethoxy, ,8- bromoethoxy, benzyloxy, methoxymethyl, ethoxymethyl, acetylmethyl or benzoylmethyl group.

The dyes of Formula I, which contain one or two formyloxy groups bound through an aliphatic intermediate member to the tertiary nitrogen atom of the amino group, exhibit superior fastness to solvents and lubricants than dyes of similar constitution, for example those disclosed in French patent specification 1,261,580, in which the molecule is free from formyloxy groups.

3,544,549 Patented Dec. 1, 1970 ice The dyes of Formula I are produced by diazotizing an amine of formula and coupling the diazonium compound with a compound of formula I NHO 0R4 (IV) In an analogous manner the dyes of Formula II are obtained by diazotization of an amine of Formula HI andcoupling of the diazonium compound with a compound of formula The coupling reaction is generally effected in an acid medium, which, if necessary, may be buttered to about pH 2.5 with, e.g., an alkali acetate, and is kept at low temperature, preferably 05 C., by cooling.

It is advantageous to convert the new dyes into dyeing preparations before application. For this purpose standard methods are employed, e.g., grinding in the presence of dispersing agents and/or filters, and the preparations are subsequently vacuum or jet dried. After the addition of an appropriate volume of water they can be dyed, padded or printed at a long or short liquor ratio as desired.

From aqueous dispersion the dyes build up excellently on textile materials of synthetic or semi-synthetic hydrophobic organic substances of high molecular weight. They are highly suitable for the dyeing and printing of textiles made of linear aromatic polyester fibres, and those of cellulose acetate or triacetate and of polyamide fibre. They are also dyeable on polyolefines, acrylonitrile polymers and polyvinyl compounds.

The known dyeing and printing methods are used, as

exemplified by those described in French patent specification 1,445,371.

Blue dyeings and prints are obtained Which have very good fastness properties, in particular to heat (i.e., sublimation, setting and pleating), solvents, lubricants and chlorine. The fastness to Water, sea water, washing and other wet tests is also very good, while the light fastness and the reserve of wool are of a notably high standard. The dyes are extremely stable to the chemicals and conditions used in the various forms of permanent press finishing. They withstand temperatures of up to about 220 C. and in particular in the range up to 140 C. without deterioration or reduction, and they are stable to acids and alkalis within the pH range of 2 to 9. Their stability to these various agencies is not adversely affected by the liquor ratio or by the presence of dyeing accelerants.

In the examples the parts are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 6.9 parts of sodium nitrite are added with vigorous stirring to parts of concentrated sulphuric acid at 6070 and, after a further 10 minutes stirring at the same temperature, the solution is cooled to 10. 26.2 parts of 1- amino-2-bromo-4,6-dinitrobenzene are then added for di- EXAMPLE 2 6.9 parts of sodium nitrite are slowly added with thorough stirring to 120 parts of concentrated sulphuric acid at 6070, andafter continued stirring for minutes at 60 the solution is cooled to 10. 26.2 parts of 1- amino-2-bromo-4,6-dinitrobenzene are added for diazotization, which is completed in 3 hours. Subsequently, 8 parts of urea are added and stirring continued for minutes at 10. The resulting diazonium-salt solution is run into a mixture of 33.8 parts of 4-acetylamino-1ethoxy-2- N,N-di-(2'-formyloxyethyl) -aminobenzene, 50 parts of glacial acetic acid and 300 parts of ice. The coupling reaction is brought to a close in acid medium, upon which the dye forms rapidly and settles out. It is filtered ofi, washed free of acid and dried. On synthetic fibres the dye gives blue dyeings having excellent fastness properties.

EXAMPLE 3 which the diazonium salt solution formed is run into a mix-.

ture of 30.5 parts of 1-ethoxy-2-N-(2'-cyanethyl)-N-(2'- formyloxyethyl) -arnino-4-fonnylaminobenzene, 100 parts of glacial acetic acid, 200 parts of ice and 10 parts of aminosulphonic acid. The coupling reaction is completed in acid medium by adjustment to pH 2.0-2.5 with sodium acetate. The dye forms immediately and settles out, to be of Formula IV. They give dyeings of blue shade on polyfiltered off, washed free of acid and dried. This dye gives dyeings of blue shade on'synthetic fibres with excellent fastness properties.

DYEING EXAMPLE 1 A fine dye powder is prepared by grinding in a ball mill for 48 hours a mixture of7 parts of the dye obtained as detailed in Example 1, 4 parts of sodium dinapht-hylmethane disulphonate,'4 parts of sodium cetyl sulphate and 5 parts of anhydrous sodium sulphate. 3.5 parts of the preparation are dispersed with a small volume of'water and the dispersion is added througha sieve to 4000 parts of water containing 2 parts of sodium lauryl sulphate to.

form the dyebath. The goods to liquor ratio is 1:40 in this particular case, but it may vary within wide limits. -100 parts of a scoured fabric of Dacron (registered trademark) polyester fibre are entered into the dyebath at 40- 50, after which 20 parts of an emulsion of a chlorinated benzene in water are added. The bath is raised slowly to and held for 1-2 hours at 95-100, after which time the fabric, which is dyed navy blue, is removed, rinsed, soaped, rinsed again and dried. The level dyeing is fast to light, cross dyeing, washing, sea water,perspiration, sublimation, burnt gas fumes, thermofixation, pleating and solvents.

DYEING EXAMPLE 2 A mixture of 40 parts of the dye obtained as given in Example 1, 55 parts of sulphite cellulose waste lye and 800 parts of water is ground in a ball mill until the dye particles are less than 1 micron in size. The colloidal solution thus formed is mixed with 25 parts of butyl glycol ether and 400 parts of 6% carboxymethyl cellulose. The paste thus obtained is highly suitablelfor the melange or Vigoureux printing of Diolen (registered trademark) polyester slubbing. This material is printed with two rollers giving a coverage of 78% and'is' steamed at without intermediate drying. -Blue prints with good fastness properties are obtained.

The dyes particularized in the following table are produced in accordance with the procedure of Example 1 from a diazotized amine of Formula III and a compound ester materials.

Example No.

X Y R R2 Same H CHzCH2OCHO CH OH Same as above 0H2oHio 0110 -CH3 Sam; as above game as above.

Same as above.

Do. 0 CH2-C6H5 I Same as above.

-CHa

Same as above; CH2CH2C1 Same as above.

Example No.

X Y R1 R2 R3 R5 do do -CH3 d0 ..C4H9 CzH5 -CH CHCH -CH2CHCH H OCHO OCHO Same Same as above Same as above C H3 Same as above.

Do. Do. H 0 CH H H OCHO V OCHO 65 do Br CH2CH:4 Same as above Same as above -CH 66: do Br Same CHzCHCHzCN -CH2CHCHCN Same as above.

' OCHO OCHO Br do Same as above Same as above H d0. -CH3 CH2CH2COOCH3 H Same as above. .A -CH3 "do CH2CN Same as above. H

OCHO

-Br do Same as above -CH2CH2COOCH2CH2OCH3 Same as above.

CH2CHZCHZOCHO -CH2CH2CH2OCHO D0. Sam; as above Same as above s Do.

do H ".do. H do. H

.d0 C a do... H ....('10 H3 Br do CH2CHCH3 Same as above.

7 OCHO 90 ..do Cl CH3 A Same as above do H 91 do Cl -CHZCH3 ---"'CH2CHCH2OCHO do CH OCHO 92 d0 Cl Same Same as above do H o.- do OCH3 60....-.. Same as above.

v 7 CN Br do CH2CH2O CHO Same as above Same as above.

Same as above do H Br dO CH2CHCH3 -..--d0 H OCHO Br ..do Same as above. do CH B1- ..do -CH2|CHCH2 C1 do Same as above.

OCHO

CH Same as above do H -CH2CH2CH2OCHO CH2CH2OH2OCHO-. H

Same as above Same as above s -CH do Same as above.

.do. do s s OCH2CH3 .do. OH GH2OOOOH Same as above. ;do .Same as above QH CH2 CH2OCHO CH2CH0CHO; Same as above. Same as above A Same as above H d do -CH2CHzCN CH3 -C1 do CH2CHCH2BI -CH2(l)H--CH2Br H OCHO OCHO -Br do CH2CHCH2OCHO CH2CH CH OCHO N0z ..do CH2CH20CHO CH2CH2CN Same as above.

Br- ..do Same as above Same as above -CH2CH2B1 Br do ..do "do C H2C1 Example No.

Formulae of representative dyes of the foregoing examples are as follows:

Br 7 OCgH; l I CHzCHzO CHO omcmo ono N02 NHCHO a Example 1;

I i CHzCHzO CHO I CHzCHzOCHO N02 NHC O CH:

Example 2;

Br OCz s /CH2CH2CN O2N- N=N N\ l CHzCHzO CHO N02 NHCHO Example 3;

Br Cz I CH2CH'2CN OzN N= N\ CH2CH2O CHO NO: NHC 0 CH3 Example 12 4;

CN 0 C211 i l /CH2CH2CN I CHzCHzOCHO Cl NHCHO Example 125;

ON OC2H I CHzCHzCN l I cmomo CHO Br NHCHO Example 126;

ON 0 C211 4 l l /CH2CH2CN 011201120 CHO Br NBC 0 CH Example 127.

. /CHzCH2OCHO 013501120 CHO N02 NHC OCH:

Example 107. Having thus disclosed the invention, what we claim is: 1. Dye of the formula 7 i l R Z o N O N 3 N/ Z I l Y wherein:

X is nitro or cyano; Y is chloro, bromo or nitro;

R is fl-formyloxyethyl, B-formyloxypropyl, y-formyloxypropyl, p,'y-diformyloxypropyl, S-formyloxy-y-chloropropyl, B-formyloxy-y-bromopropyl or p-formyloxy-vcyanopropyl;

R is methyl, ethyl, propyl, butyl, cyanalkyl, alkoxycarbonylalkyl or one of the meanings of R each alkyl and alkoxy containing 1, 2, 3, or 4 carbon atoms; and

R is a hydrogen atom, alkyl or alkoxy; each alkyl and alkoxy containing 1, 2, 3, or 4 carbon atoms and any substituent thereon being a non-water-solubilizing substitnent selected from the group consisting of chloro, bromo, cyano, methoxy, ethoxy, phenoxy, phenyl, acetyl and benzoyl.

2. A dye according to claim 1 of the formula NHCORQ cyanomethyl, phenoxymethyl fl-chloroethoxy, B-bromo-,

ethoxy, benzyloxy, methoxymethyl, ethoxymethyl, acetylmethyl or benzoylmethyl group.

3. The-dye according to claim 1 of the formula Br 7 002 /CH2CH2OCHO OzN N=N CHzCHaOCHO V NO: 7 NHCHO 4. The dye according to claim 1 of the formula B1 0 C3H5 I l /CH:CH:O 0110 I CHzCH2O CHO N0: NHCO on 5. The dye according to claim 1 of the formula Br oCz s l /CH2CH2CN l GHzCHzOCHO N02 NHCHO 6. The dye according to claim 1 of the formula l NH 0 CH3 CHzCHzCN CHzCHzO CH0 7. The dye according to claim 1 of the formula NHCHO OHzCHzCN CHzCHzO CH0 8. The dye according to claim 1 of the formula NHCHO CHzCHzCN CHzCHzO CHO 9. The dye according to claim 1 of the formula 1 i CHzCHzCN l CHzCHzO CHO Br NHOOCHQ 10. The dye according to claim 1 of the formula ON OC2H I CH2CH2O CHO NHCOCHa References Cited UNITED STATES PATENTS CH2OH2OCHO JOSEPH P. BRUST, Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,544,549 Dated July 31 1967 Inventor(s) RUEDI ALTERMATT et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 52, in the formula "R should read --R Column 2, line "filters" should read --fillers--. Column 3, Example 14, the definition 01 should read --do--. Column 4, Example 8, in the definition of R "d" shot read --do-. Column 5, Example 50, "CH" should read -CN-. Column 6, in [heading of the last column, "R should read -R Column 8, line 28, "I

should read --R Signed and sealed this 1 8th day of July 1 972.

(SEAL) Attest:

EDWARD M.FLEICHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

